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. Chlorine-initiated oxidation of n -alkanes ( C8−12 ) under high-nitrogen oxide conditions was investigated. Observed secondary organicaerosol yields (0.16 to 1.65) are higher than those for OH-initiatedoxidation of C8−12 alkanes (0.04 to 0.35). A high-resolutiontime-of-flight chemical ionization mass spectrometer coupled to a FilterInlet for Gases and AEROsols (FIGAERO–CIMS) was used to characterize the gas-and particle-phase molecular composition. Chlorinated organics were observed,which likely originated from chlorine addition to the double bond present onthe heterogeneously produced dihydrofurans. A two-dimensional thermogramrepresentation was developed to visualize the composition and relative volatilityof organic aerosol components using unit-mass resolution data. Evidence ofoligomer formation and thermal decomposition was observed. Aerosol yield andoligomer formation were suppressed under humid conditions (35 % to67 % RH) relative to dry conditions (under 5 % RH). The temperatureat peak desorption signal, Tmax , a proxy for aerosol volatility,was shown to change with aerosol filter loading, which should be constrainedwhen evaluating aerosol volatilities using the FIGAERO–CIMS. Results suggestthat long-chain anthropogenic alkanes could contribute significantly toambient aerosol loading over their atmospheric lifetime.

atmospheric chemistry and physics

Chlorine-initiated oxidation of &amp;lt;i&amp;gt;n&amp;lt;/i&amp;gt;-alkanes under high-NO&amp;lt;sub&amp;gt;&amp;lt;i&amp;gt;x&amp;lt;/i&amp;gt;&amp;lt;/sub&amp;gt; conditions: insights into secondary organic aerosol composition and volatility using a FIGAERO–CIMS